The invention relates to novel hydroxy and amino-functional polyahls containing carbonate, urethane, and/or urea moieties.
Stevens (in U.S. Pat. Nos. 3,248,414; 3,248,415; and 3,248,416) discloses the preparation of poly(alkylene carbonate) polyols from (1) carbon dioxide and 1,2-epoxides; (2) cyclic carbonates such as ethylene carbonate; or (3) cyclic carbonates and a 1,2-epoxide. A minor amount of a polyol is employed as an initiator.
U.S. Pat. No. 3,248,415 to Stevens discloses that certain polyamines can be used as initiators in reactions with alkylene carbonates or alkylene oxides and carbon dioxide. These polyamines, described at column 6, lines 33-57, include: other organic compounds having at least 2 active hydrogens usually from 2 to 4 active hydrogens are of use. By active hydrogen is meant a hydrogen linked directly to a nitrogen, sulfur or oxygen atom such as is found in hydroxyl, non-tertiary amino, mercapto, carbamate and carboxyl groups. Each active hydrogen as herein intended is linked to a different nitrogen, sulfur or oxygen atom in the compound.
Polyamines, especially diamines in which the amino groups are primary or secondary including ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and the like are suitable organics containing 2 active hydrogens. Piperazine and like polyamines wherein each of the nitrogens have but one hydrogen linked thereto (secondary amino nitrogens) are preferred. Alkylol amines such as ethanolamine and diethanolamine are illustrative of organics having 2 or more active hydrogens contributed by hydrogens linked to different atoms, e.g. nitrogen and oxygen.
Very similar language is used by Stevens in U.S. Pat. No. 3,248,416, at column 3, lines 38-61.
Maximovich (U.S. Pat. No. 3,896,090) reacted ethylene carbonate with diethylene glycol and treated the reaction product under reduced pressure to remove the unreacted ethylene carbonate and diethylene glycol.
Maximovich discloses at column 2, lines 60-66 and at column 3, lines 21-28, the use of organic compounds used in conjunction with the epoxide or alkylene carbonate. Maximovich discloses organic compounds having 2 or more active hydrogens, e.g., a monomeric polyol, such as is found in hydroxy, nontertiary amino, mercapto, and carboxyl groups, as well as polyamines, mercaptans, alkylolamines, and the like.
A variety of different workers have reported materials where only one of the moieties selected from the group of carbonate, urethane and urea is present in the backbone of the molecule. Representative carbonate examples are given in copending Dow application Ser. No. 750,362, filed July 1, 1985. Procedures have been developed by Yamazaki and Nakahama, Polymer Preprints (ACS, Div. Polym. Chem,) 20 (1) 146 (1979) which produce materials with carbonate, urethane or urea moieties in the backbone, However, their procedures neither yield materials with two or more different moieties selected from this group nor anticipate the use of alkyleneoxy units in the polymer backbone. Representative urea examples can be found in U.S. Pat. Nos. 4,002,598; 4,115,360; 4,116,938; 4,178,427 and West German 2,748,705. These materials have only amino end groups.
C. Giori, Polymer Preprints (ACS, Div. Polym. Chem.) 11 (1) 326 (1970) has studied the reactions of aminophenols and amino alcohols with phosgene in pyridine as solvent. Even though the bulk of his work involved aromatic systems, he did a limited amount of work with aliphatic systems. He studied ethanolamine, without success (no polymer), obtaining only the cyclic product, 2-oxzolinone. The only other aliphatic system which he studied was 1,6-aminohexanol. This system successfully produced polymer which contained both carbonate and urea moieties in the backbone. However, Giori states on p. 327 "According to these reactions, free amine groups, if present, will disappear from the system." This is stated to occur at ambient temperature. Therefore, this material produced by Giori does not meet the third criteria of the present invention since it does not have, on the average, end groups containing both hydroxyl and amino functionally. In addition, Giori's procedure yields alternate poly(carbonate-urea) structures not the random structures of the instant invention. Also, Giori did not disclose the use of alkyleneoxy units in the polymer backbone.